Remediation of toxins in biorefinery process streams

ABSTRACT

Provided are methods and systems for remediating toxins present in feedstock that are used in processes to produce ethanol and other products.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation patent application of nonprovisionalpatent application Ser. No. 18/107,163 filed on Feb. 8, 2023, which is acontinuation patent application of nonprovisional patent applicationSer. No. 17/377,130 filed on Jul. 15, 2021, which is a divisional patentapplication of nonprovisional patent application Ser. No. 16/050,681filed on Jul. 31, 2018, now U.S. Pat. No. 11,076,621, which in turnclaims the benefit of U.S. Provisional Patent Application Ser. No.62/539,226, filed Jul. 31, 2017, wherein the disclosure of each patentapplication is incorporated in its entirety herein by reference.

FIELD OF THE INVENTION

The invention relates to systems and methods for remediation of toxinsin biorefinery process streams.

BACKGROUND

Cereal grains are often used as feedstock for the production of targetchemicals in a biorefinery. The cereal grains are typically milled andfurther processed to convert starch and/or cellulose contained in thegrains into fermentable sugars. The sugars are then converted into thetarget chemicals by microorganisms, such as yeasts, in a fermentationprocess. The fermentation product includes the target chemical and othermaterials which may include for example, water and other components suchas oils, proteins, and residual carbohydrates including starches,sugars, and fiber. The target chemical is separated from thefermentation product and the other components are often collected as oneor more co-products. An important class of co-products is nutritionalproducts. The value of nutritional co-products is affected bycontaminants that pass through the biorefinery process and into theco-product. For example, cereal grains can become infected withpathogens that produce a variety of toxins known as mycotoxins. Thereare many mycotoxins including, for example, various aflatoxins,ochratoxin, citrinin, ergo alkaloids, patulin, and fusarium toxinsincluding for example zearalenone, deoxynivalenol, and fumonisin amongothers. The presence or severity of toxins in cereal grains is affectedby the growing conditions for a particular location in a particularyear. What is needed is an economical way to effectively reduce oreliminate toxins from biorefinery co-products.

The present invention provides for the remediation of toxins inbiorefinery co-products by treating biorefinery process streams with atoxin mitigant.

The biorefinery feedstock may include cereal grains such as, forexample, corn, wheat, sorghum, and rice among others.

The remediation may involve, for example, introducing a treatmentcompound into one or more process streams during or between processsteps that will react with the toxin. For example, the treatmentcompound may be a sulfur containing compound such as a sulfate, sulfite,bisulfite, metabisulfite, and others. For example, the treatmentcompound may be ammonium bisulfite, potassium bisulfite, sodiumbisulfite, and others. These compounds will react with some toxins toform less toxic or non-toxic sulfur compounds. For example,deoxynivalenol (DON) will react with sodium bisulfite to form sulfonatedderivative of DON, termed as DON sulfonate or DONS.

Process steps may include one or more of inputting feedstock into thebiorefinery, milling the feedstock to a meal or flour, mixing of themilled material with water to form a slurry, heating of the slurry toliquefy one or more components of the slurry, enzymatically hydrolyzingcomponents of the slurry, fermenting the slurry, collecting thefermentation product, separating the fermentation product into differentcomponents, collecting fermentation product streams, dewatering, andcollecting co-products. Not all of these steps need be used in anyparticular biorefinery operation.

SUMMARY

The present invention provides for the remediation of toxins inbiorefinery co-products by treating biorefinery process streams with atoxin mitigant.

The biorefinery feedstock may include cereal grains such as, forexample, corn, wheat, sorghum, and rice among others.

The remediation may involve, for example, introducing a treatmentcompound into one or more process streams during or between processsteps that will react with the toxin. For example, the treatmentcompound may be a sulfur containing compound such as a sulfate, sulfite,bisulfite, metabisulfite, and others. For example, the treatmentcompound may be ammonium bisulfite, potassium bisulfite, sodiumbisulfite, and others. These compounds will react with some toxins toform less toxic or non-toxic compounds. For example, deoxynivalenol(DON) will react with sodium bisulfite to form sulfonated derivative ofDON, termed as DON sulfonate or DONS.

Process steps may include one or more of inputting feedstock into thebiorefinery, milling the feedstock to a meal or flour, mixing of themilled material with water to form a slurry, heating of the slurry toliquefy one or more components of the slurry, enzymatically hydrolyzingcomponents of the slurry, fermenting the slurry, collecting thefermentation product, separating the fermentation product into differentcomponents, collecting fermentation product streams, dewatering, andcollecting co-products. Not all of these steps need be used in anyparticular biorefinery operation.

In one aspect of the invention is a process for remediating mycotoxin inone or more biorefinery process streams, wherein the process comprisesintroducing one or more treatment compounds into at least one grainbiorefinery process stream to form a treated grain biorefinery processstream, wherein the at least one grain biorefinery process streamcomprises a mycotoxin in a first amount, wherein the one or moretreatment compounds react with the mycotoxin to form a treatedmycotoxin, and wherein the treated grain biorefinery process streamcomprises the mycotoxin in a second amount, wherein the second amount isless than the first amount.

In another aspect of the invention is a system for remediating toxinscomprising: a reactant storage system comprising one or more treatmentcompounds; and a metering system in fluid communication with thereactant storage system, wherein the system is adapted to be coupled toone or more grain biorefinery process streams to add a controlled amountof the one or more treatment compounds into the one or more grainbiorefinery process streams, to produce a treated grain biorefineryprocess stream, wherein the at least one grain biorefinery processstream comprises a mycotoxin in a first amount, wherein the one or moretreatment compounds reacts with the mycotoxin to form a treatedmycotoxin, and wherein the treated grain biorefinery process streamcomprises the mycotoxin in a second amount, wherein the second amount isless than the first amount.

BRIEF DESCRIPTION OF THE DRAWINGS

Various examples of the present invention will be discussed withreference to the appended drawings. These drawings depict onlyillustrative examples of the invention and are not to be consideredlimiting of its scope.

FIG. 1 is a flow diagram of a cereal grain-to-ethanol conversionprocess.

FIG. 2 is a flow diagram of a toxin remediation system.

FIG. 3 is a flow diagram of a toxin remediation system connected to aprocess stream.

FIG. 4 is a graphical representation of sodium bisulfate dose (SBS) anddeoxynivalenol (DON).

FIG. 5 is a graphical representation of reduction in DON in response todwell time.

FIG. 6 is a graphical representation of DON amount in syrup for twodifferent bisulfites.

FIG. 7 is a graphical representation of DON present in DDGS in agrain-to-ethanol conversion process.

DESCRIPTION

Described herein are methods and systems to reduce the toxicity, theconcentration, or both (referred herein as “remediation”) of one or moretoxins present in feedstock used in biorefinery processes. “Biorefinery”as used herein refers to a facility that processes biological material(such as seed, grain, crop waste or feedstock) to produce products suchas as ethanol, and other products such as animal feed (dried distiller'sgrain).

One example of the invention is shown in FIG. 1 depicting an ethanolbiorefinery operation 100 that produces animal feed as a co-product.Grain 102 that has been contaminated with toxin is used as feedstock forthe production of ethanol in the biorefinery. The grain 102 is reducedin size in a milling system 104. The milled grain 106 is mixed withwater and further treated, for example thermally and/or enzymatically,to convert starch and fiber into fermentable sugars in asaccharification system 108. The resulting slurry 111 is combined withan ethanologen (e.g. yeast) to convert the sugars into ethanol in afermentation system 112. In embodiments, the saccharification andfermentation can occur simultaneously in a single system (e.g. in an SSFfermentation system). The fermentation product, or beer 114, includesethanol, water, oil, dissolved solids, toxin, protein, yeast, andresidual carbohydrates including starch, sugar, and fiber. The beer 114may be collected in a beer storage system 116 prior to furtherprocessing. The beer 114 is distilled in a distillation system 118 toseparate the ethanol 120 from the other components, called wholestillage 122, of the beer 114. The whole stillage 122 is processed in astillage separation system 124 into cake 126 and thin stillage 128. Thecake 126 contains more of the solid particulate matter from the beer 114including fiber, protein, yeast, and residual solid starch and someliquid including water, oil, and dissolved solids. The thin stillage 128contains more of the liquid from the beer 114 including water, oil, anddissolved solids. The toxin is distributed in the cake 126 and thinstillage 128. However, because the toxin is water soluble, more of it iscontained in the thin stillage 128. The thin stillage 128 isconcentrated in an evaporation system 130 to form syrup 132. The syrup132 may be collected in a syrup storage system 133 prior to furtherprocessing. The syrup 132 and cake 126 may be combined and dried in adrying system 134 to produce dried distillers grain with solubles (DDGS)136. Examples of biorefinery operations are described in U.S. Pat. Nos.7,842,484, 8,409,640, 7,919,291, 8,470,550, 8,748,141, 8,679,793,8,597,919, 8,702,819, 4,092,434, and 4,316,956 all of which are herebyincorporated by reference.

In the example of FIG. 1 , a treatment compound (e.g. sulfur compound)is introduced into a process stream of the biorefinery operation. Thetreatment compound combines with the toxin to form a less toxic ornon-toxic compound. Since the toxin enters the biorefinery with thegrain, it is present in many of the biorefinery process streams and thetreatment compound may be introduced to any of these streams to reactwith the toxin. For example the treatment compound may be introduced ina stream 202 that mixes with the grain 102 prior to or during milling.The treatment compound may be introduced in a stream 204 that mixes withthe milled grain 106 prior to or during saccharification 108. Thetreatment compound may be introduced in a stream 206 that mixes with theslurry 111 prior to or during fermentation 112. The treatment compoundmay be introduced in a stream 208 or 210 that mixes with the beer 114prior to or during distillation 118. The treatment compound may beintroduced in a stream 212 that mixes with the whole stillage 122 priorto or during stillage separation 124. The treatment compound may beintroduced in a stream 214 that mixes with the thin stillage prior to orduring evaporation 130. The treatment compound may be introduced in astream 216 or 217 that mixes with the syrup prior to or during drying134. The treatment compound may be introduced in a stream 218 that mixeswith cake prior to or during drying 134. The treatment compound may beintroduced in a stream 220 that mixes with the DDGS.

While introduction of the treatment compound in any one or more of thestreams 202, 204, 206, 208, 210, 212, 214, 216, 217, 218, 220 mayremediate the toxin, the present inventors have found that certainfactors enhance the effectiveness of the remediation. It has been foundthat mixing in an aqueous environment facilitates the reaction. It haslikewise been found that elevated temperature facilitates the reaction.Similarly, less volume of the treatment compound solution is required ifa stream is chosen in which the toxin has been concentrated. The presentinventors have found that toxin levels are concentrated three to fivetimes in DDGS in an ethanol operation. Most of the one or more toxinsare concentrated via the thin stillage to syrup process stream. Inaddition, it may be desirable not to introduce the treatment compoundinto the fermentation system 112 so as not to introduce changes in thecarefully controlled fermentation environment. Similarly, it may bedesirable not to introduce the treatment compound into the distillationsystem 118 to avoid any additional material that might deposit ondistillation system equipment. A portion of the thin stillage is oftenused as recycled water that is fed back to a prior process step, such assaccharification 108 and/or fermentation 112 as shown for example at222, and it may be desirable to avoid recycling treatment compound to aprior process step. For these reasons, it is preferable to introduce thetreatment compound into the hot, aqueous thin stillage or syrup, wheremost of the toxin is concentrated, after any recycled thin stillage hasbeen drawn off for recycle water purposes but before the DDGS has beenfully dried. It may also be desirable not to introduce the treatmentcompound into the evaporation system 130 to avoid any additionalmaterial that might deposit on evaporation equipment. It is believedthat introducing the treatment compound into the syrup via stream 216may be most advantageous. Wherever the treatment compound is introduced,the reaction may benefit from increased dwell time such as, for example,the dwell time of the syrup in the syrup storage system 133.

The treatment compound may be introduced via a toxin remediation system300 as shown in FIG. 2 . In the example of FIG. 2 , the toxinremediation system 300 includes a reactant storage system 302 containingan aqueous solution of the treatment compound and a metering system 304in fluid communication with the reactant storage system 302 and thedesired introduction point in the process stream. For example, themetering system 304 may connect directly to any one or more of thestreams 202, 204, 206, 208, 210, 212, 214, 216, 217, 218, 220. Forexample, the toxin remediation system 400 of FIG. 2 may be a skidmounted self-contained unit that is inserted into an existing processstream in an existing operation to provide for toxin remediation Toxinlevels may be monitored and a controller may be used to control themetering system to deliver a dose of treatment compound sufficient toreduce toxin levels to an acceptable threshold (e.g. values as reportedby the US Food & Drug Administration (FDA)). Toxin levels may bemonitored at any point in the biorefinery operation. For example thetoxin level in incoming grain may be monitored and a dose may becalculated based on those levels. In another example, the toxin levelmay be monitored in the DDGS and the toxin remediation system controlledto maintain the DDGS toxin level within an acceptable range. In anotherexample the toxin level may be monitored in a process stream upstream ofthe toxin remediation system and also in a process stream downstream ofthe toxin remediation system. Alternatively, monitoring may be omittedand a sufficient dose of treatment compound may be administered to treatmaximum expected values of toxins. At times when no toxin is present thetoxin remediation system can be idled to stop the flow of treatmentcompound to conserve treatment compound and reduce costs. For example,grain may be tested prior to entry into the biorefinery, and in cropyears and regions where toxins are present above a threshold value theremediation system can be employed.

Depending on the time for reacting and the other considerations, thedosing of the treatment compound can be conducted in a batch process ora continuous process.

FIG. 3 depicts a toxin remediation system 400 configured to be connectedin line with a process stream. For example, the toxin remediation system400 of FIG. 3 may be a skid mounted self-contained unit that is insertedinto an existing process stream in an existing operation to provide fortoxin remediation. In the example of FIG. 3 , the toxin remediationsystem 400 includes an inlet 402, an outlet 404, a reactant storagesystem 406 containing an aqueous solution of the treatment compound, ametering system 408 in fluid communication with the reactant storagesystem 406, and a mixing system 410 in fluid communication with theinlet 402, the metering system 410 and the outlet 404. The toxinremediation system 400 may be connected to a biorefinery operation byconnecting an upstream process step to the inlet 402 and connecting theoutlet 404 to a downstream process step. The toxin remediation system400 may include one or more sensing or sampling systems 412, 414. Forexample the toxin level at the inlet may be monitored and communicatedto the metering system 408 where it may be used to adjust the flow rateof the treatment compound. Likewise, the toxin level at the outlet maybe monitored and communicated to the metering system 408 where it may beused to adjust the flow rate of the treatment compound. At times when notoxin is present the toxin remediation system can stop the flow oftreatment compound to conserve treatment compound and reduce costs. Thesensing or sampling systems 412, 414 are not required and it isanticipated that grain will be sampled and tested for the presence oftoxins before entry into the biorefinery. Grain samples may beperiodically taken and tested. Likewise, a process stream, e.g. DDGS,may be periodically tested to determine the need for and/oreffectiveness of toxin remediation.

While most of the application describes the process with respect tograin, other feedstocks are also within the scope of this application.Feedstock includes seed, grains and other feedstock. For example, grainsinclude cereal grains such as corn, wheat, barley, rice, sorghum, andrye. Further, while the production of ethanol is described, due to itsparticular utility as a fuel, any process that converts a feedstock intoa target chemical and a nutritional co-product (e.g. animal feed) isconsidered within the scope of this application.

The compounds, compositions, and methods described herein can reduce ormake non-toxic a variety of toxins. In embodiments, the toxin is one ormore mycotoxins. Mycotoxins are toxic fungal metabolites, often found inagricultural products that are characterized by their ability to causehealth problems for humans and animals. Mycotoxins include compoundssuch as aflatoxins, ochratoxins, patulin, fumonisins, zearalenones, andtrichothecenes. They are produced for example by different Fusarium,Aspergillus, Penicillium and Alternaria species.

Examples of trichothecene mycotoxins include T-2 toxin, HT-2 toxin,isotrichodermol, diacetoxyscirpenol (DAS), 3-deacetylcalonectrin, 3,15-dideacetylcalonectrin, scirpentriol, neosolaniol;15-acetyldeoxynivalenol, 3-acetyldeoxynivalenol, nivalenol,4-acetylnivalenol (fusarenone-X), 4, 15-diacetylnivalenol,4,7,15-acetylnivalenol, and deoxynivalenol (DON, also known asvomitoxin), and their various acetylated derivatives. The most commontrichothecene in Fusarium head blight is deoxynivalenol produced forexample by Fusarium graminearum and Fusarium culmorum.

In embodiments, the reaction between a treatment compound and toxinresults in a less toxic or non-toxic toxin. In embodiments, thetreatment compound is a sulfur oxyanion. In embodiments, the treatmentcompound is a sulfur containing compound such as sulfate, sulfite,bisulfite, metabisulfite or combination thereof. In embodiments thetreatment compound is ammonium bisulfite, potassium bisulfite, sodiumbisulfite, or combination thereof.

In embodiments, the treatment compound is introduced into one or morebiorefinery streams or systems by reacting the toxin and treatmentcompound for a dwell time of between 1 second to about 24 hours. Inembodiments, the dwell time is less than 10 minutes. In embodiments, thedwell time is greater than 24 hours. In embodiments, the treatmentcompound is introduced into one or more biorefinery streams or systemsby reacting the toxin and treatment compound for a dwell time of about 1second to 1 minute, from about 1 minute to about 5 minutes, from about 5minutes to 180 minutes, from about 10 minutes to 30 minutes, from about30 minutes to 60 minutes, from about 60 minutes to 90 minutes, or fromabout 90 minutes to 180 minutes. In embodiments, the treatment compoundis introduced into one or more biorefinery streams or systems byreacting the toxin and treatment compound for a dwell time of about 1hour to 24 hours, from 1.5 hours to 5 hours, from 5 hours to 12 hours,or from 12 hours to 24 hours.

In embodiments, treatment compound is introduced into one or morebiorefinery streams by reacting the toxin and treatment compound at atemperature from about 30° C. to 120° C., 30° C. to 60° C., 35° C. to80° C., 45° C. to 90° C., 50° C. to 100° C., or 55° C. to 120° C. toresult in a treated biorefinery process stream.

In embodiments, the treated biorefinery process streams are wholestillage, thin stillage, syrup, cake, dried distiller's grain, orcombination thereof. In embodiments, the treated biorefinery processstream is syrup. In embodiments, the treated biorefinery process streamis syrup. In embodiments, the treated biorefinery process stream isdried distiller's grain with solubles (DDGS).

In embodiments, the biorefinery process stream is an aqueous streamhaving a solids content of less than 90%, less than 75%, less than 60%,less than 50%, less than 40%, less than 30%, less than 20%, less than10%, less than 5% by weight. In embodiments, the biorefinery processstream has a solids content of 5-60%, 15-40%, 35-50%, 40-60% by weight.

In embodiments, the treatment compound is added to one or morebiorefinery process streams from about 0.05% to about 5% weight of thebiorefinery stream. In embodiments, the treatment compound includes asulfur containing compound and the dose is limited such that the sulfurin the final product, e.g. DDGS, is no more than an acceptable thresholdvalue. For example, the amount of sulfur in DDGS may be limited to beless than 5%; less than 3%; or even less than 1% by weight of the DDGSon a dry weight basis. In embodiments, the treatment compound dose islimited so that the sulfur in the DDGS is increased by the treatment byno more than 0.5% by weight of the DDGS on a dry weight basis.

In embodiments, the reaction is between a sulfur oxyanion and DON e.g.between a sulfite and a DON to result in a treated DON-sulfonate. Inembodiments, the treatment compound is dry powdered SBS and is suppliedin an amount from about 0.01 to about 0.1, e.g. from about 0.02 to about0.05 grams SBS per dry gram syrup, or equivalent dose. In embodiments,the treatment compound is a 38% aqueous solution of SBS and is suppliedin an amount from about 0.5 gallons per minute and about 2.0 gallons perminute; e.g. from about 1.0 to about 1.5 gallons per minute to a syrupstream in a commercial scale biorefinery. In embodiments, the treatmentcompound is a 38% aqueous solution of SBS and is supplied in an amountbetween 0.05% to about 5% weight of the biorefinery process stream. Inembodiments, the treatment compound is a 38% aqueous solution of SBS andis supplied in an amount between 0.05% to about 5% weight of the syrupprocess stream.

In embodiments, the concentration of the toxin after treatment with thetreatment compound is reduced by 30% or more or from about 30-99%, from30-60%, from 45% to 75%, or from 70% to 99% of the toxin beforeintroduction of the treatment compound.

In embodiments, the treated mycotoxin is reduced by 30% or more or fromabout 30-99%, from 30-50%, from 45%-75%, or from 70%-99% of theuntreated, initially present toxin. In embodiments, the mycotoxin (e.g.DON) is reduced by 30% or more or from about from 30-50%, from 45%-75%,or from 70%-99% of the untreated, initially present toxin.

In embodiments, the mycotoxin (e.g. DON) in the treated biorefinerystream (e.g. syrup) is reduced to less than 5 ppm, less than 1 ppm, orfrom 5-1 ppm with a dwell time of minutes. Depending on the mycotoxinand the specifications for the mycotoxin amount, the described methodcan also be used to reduce the mycotoxin to as low as 1 ppb.

In embodiments, the mycotoxin (e.g. DON) in the treated biorefineryprocess stream (e.g. syrup) reduced to less than 1 ppm at 30 minutesdwell time. It is expected that dwell times of less than 30 minutes willeffectively reduce DON levels to acceptable values. For example, dwelltimes of less than 10 minutes, less than 5 minutes, or even less than 1minute are expected to provide effective mycotoxin reduction. It is notnecessary to reduce the DON to less than 1 ppm. For example, the FDAadvises a DON limit for DDGS of 30 ppm, less than 10 ppm in total rationfor ruminating beef cattle and feed lot beef cattle older than fourmonths. The FDA advises a DON limit for DDGS of 30 ppm, less than 5 ppmin total ration for dairy cattle older than 4 months. The FDA advises aDON limit for grains and grain by-products of 5 ppm, less than 20% ofdiet for swine.

In embodiments, the DON in the treated syrup stream is reduced to lessthan 1 ppm at minutes dwell time, less than 10 minutes, less than 5minutes, or even less than 1 minute.

In embodiments, the DON in the treated biorefinery process stream e.g.DDGS reduced to less than 1 ppm at 30 minutes dwell time, less than 10minutes, less than 5 minutes, or even less than 1 minute.

Remediation of toxins in biorefinery process streams according to thedescribed process preserves the value of DDGS that would otherwise bedegraded by the presence of toxins in the feedstock or grain. Suchremediation may also reduce input costs to the biorefinery operation bypermitting the use of grain that has been discounted due to the presenceof toxins. Such remediation may also improve grain usage by facilitatingthe use of grain that would otherwise go to waste. The toxin remediationsystem described herein requires a relatively low capital investment andrelatively low operating expense. The system may be monitored andmetered so that it consumes treatment compound and operates equipmentonly when and only to the degree needed. Additional embodiments includethe following:

-   -   1. A process for remediating mycotoxin in one or more        biorefinery process streams, wherein the process comprises        introducing one or more treatment compounds into at least one        grain biorefinery process stream to form a treated grain        biorefinery process stream, wherein the at least one grain        biorefinery process stream comprises a mycotoxin in a first        amount, wherein the one or more treatment compounds react with        the mycotoxin to form a treated mycotoxin, and wherein the        treated grain biorefinery process stream comprises the mycotoxin        in a second amount, wherein the second amount is less than the        first amount.    -   2. The process of embodiment 1, wherein the treated mycotoxin is        less toxic than the mycotoxin in the first amount.    -   3. The process as in one of embodiments 1-2, wherein the treated        mycotoxin is nontoxic.    -   4. The process as in one of embodiments 1-3, wherein the        biorefinery process stream comprises a grain-to-ethanol        conversion process.    -   5. The process as in one of embodiments 1-4, wherein the at        least one grain biorefinery process stream is produced by the        steps of:        -   i. milling the grain to provide a milled grain;        -   ii. mixing the milled grain with water to form a slurry;        -   iii. saccharifying the slurry;        -   iv. fermenting the saccharified slurry with a yeast to            produce a beer;        -   v. separating the beer to produce an ethanol stream and a            solids stream; and        -   vi. drying the solids stream to produce dried distillers            grain.    -   6. The process as in one of embodiments 1-5, wherein the at        least one grain biorefinery process stream is a milled grain, a        slurry, a beer, a whole stillage, a thin stillage, a syrup, a        cake, a dried distiller's grain or combination thereof.    -   7. The process as in one of embodiments 1-6, wherein the grain        is a cereal grain.    -   8. The process as in one of embodiments 1-7, wherein the grain        is corn, wheat, rye, barley, rice or sorghum.    -   9. The process as in one of embodiments 1-8, wherein the        mycotoxin comprises at least one aflatoxin, ochratoxin,        citrinin, ergo alkaloids, patulin, or fusarium toxins.    -   10. The process as in one of embodiments 1-9, wherein the        mycotoxin comprises at least one deoxynivalenol.    -   11. The process as in one of embodiments 1-10, wherein the        treatment compound includes a sulfur oxyanion.    -   12. The process of claim 11 wherein the sulfur oxyanion is a        sulfate, a sulfite, a bisulfite or a metabisulfite.    -   13. The process as in one of embodiments 1-12, wherein the        treatment compound is an ammonium bisulfite, potassium        bisulfite, sodium bisulfite, or combination thereof    -   14. The process as in one of embodiments 1-13, wherein the        treatment amount is between to about 5% weight of the        biorefinery process stream.    -   15. The process as in one of embodiments 1-14, wherein the        introducing the one or more treatment compounds into the at        least one grain biorefinery process stream comprises a dwell        time of from 1 hour to 24 hours between the introducing and        producing the dried distillers grains.    -   16. The process as in one of embodiments 1-15, wherein the        introducing the one or more treatment compounds into the at        least one biorefinery process stream is at temperatures from        30° C. to 120° C.    -   17. The process as in one of embodiments 1-16, wherein the one        or more biorefinery process stream comprises 5 to 60% solids by        weight.    -   18. The process as in one of embodiments 1-17, wherein the        mycotoxin in the second amount is reduced by 30% or more as        compared to the mycotoxin in the first amount.    -   19. The process as in one of embodiments 1-18, wherein the        treated grain biorefinery process stream is a whole stillage,        thin stillage, syrup or combination thereof    -   20. The process as in one of embodiments 1-19, wherein the        treated grain biorefinery process stream has a concentration of        mycotoxin of less than 5 ppm.    -   21. The process as in one of embodiments 1-20, wherein the        treated mycotoxin comprises a deoxynivalenol sulfonate.    -   22. A composition produced by the process as in one of        embodiments 1-21.    -   23. A system for remediating toxins comprising:        -   a reactant storage system comprising one or more treatment            compounds; and        -   a metering system in fluid communication with the reactant            storage system, wherein the system is adapted to be coupled            to one or more grain biorefinery process streams to add a            controlled amount of the one or more treatment compounds            into the one or more grain biorefinery process streams, to            produce a treated grain biorefinery process stream, wherein            the at least one grain biorefinery process stream comprises            a mycotoxin in a first amount, wherein the one or more            treatment compounds reacts with the mycotoxin to form a            treated mycotoxin, and wherein the treated grain biorefinery            process stream comprises the mycotoxin in a second amount,            wherein the second amount is less than the first amount.    -   24. The system of claim 23 further comprising a mixing system in        fluid communication with an inlet and an outlet of one or more        grain biorefinery process streams and the metering system.    -   25. The system as in one of embodiments 23-24 further connected        to one or more of:        -   a milling system, wherein the milling system mills a            feedstock to provide a milled material;        -   a saccharification system for converting the slurry into            sugar, wherein the saccharification system is in fluid            communication with the milling system;        -   a fermentation system comprising yeast and in fluid            communication with the saccharification system, the            fermentation system converts the sugar into a beer;        -   a distillation system in fluid communication with the            fermentation system, wherein the distillation system can            distill the beer to form a distillate comprising the alcohol            and a solids stream; and        -   a separation system in fluid communication with the solid            stream to produce dried distillers grain.

EXAMPLE 1

Experiments were performed that demonstrated that sodium bisulfite (SBS)was effective at reducing the measurable quantity of deoxynivalenol(DON) in syrup by the NEOGEN™ VERATOX™ for DON 2/3 kit. Initial testingresulted in reductions in DON. Treating syrup with SBS at processtemperatures for extended time periods resulted in a DON reduction ofgreater than 85% in the syrup stream. Encouraged by these initial testresults, further testing was performed utilizing a design of experimentsto determine an equation modeling the effect of time, temperature, andSBS in the treatment of syrup. Syrup from a corn ethanol biorefinery wasobtained and processed in the laboratory. All thermal treatments wereperformed utilizing a Parr 4560 reactor and a combined total of 70 g ofsyrup and SBS per reaction. Reaction conditions were from 85 ° C. to 115° C.; for 2 to 6 hours; and 0 to 0.05 g sodium bisulfite per dry gramsyrup. The results from this study indicated a correlation between theSBS loading and the reduction in syrup DON. The model predicts a greaterthan 85% reduction in syrup DON is likely if treatment in a commercialprocess syrup tank is utilized. It was calculated that at a plant thatis currently producing DDGS with 14.5 ppm DON with a 95% reduction insyrup DON would produce DDGS with 4.6 ppm DON.

EXAMPLE 2

Syrup from a corn ethanol biorefinery was obtained and processed in thelaboratory. Treatment was performed utilizing a Parr 4560 reactor and acombined total of 70 g of syrup and SBS per reaction. The reactioncondition was carried out at 50° C. for 120 minutes and varying amountsof sodium bisulfite per dry gram syrup. The DON was measured by NEOGEN™VERATOX™ for DON 2/3 kit.

FIG. 4 showed that as the SBS dose increased, the DON was reduced in thetreated syrup.

EXAMPLE 3

Syrup from a corn ethanol biorefinery was obtained and processed in thelaboratory. Treatment was performed utilizing a Parr 4560 reactor and acombined total of 70 g of syrup and SBS per reaction. The reactioncondition was carried out at 85° C. for 30 minutes to 180 minutes using0.048 grams sodium bisulfite per dry gram syrup. The DON was measured byNEOGEN™ VERATOX™ for DON 2/3 kit.

FIG. 5 showed that the DON in the treated syrup reduced to less than 1ppm at 30 minutes dwell time.

EXAMPLE 4

Syrup from a corn ethanol biorefinery was obtained and processed in thelaboratory using a Parr 4560 reactor and combined with either 0.048grams of SBS or ammonium bisulfite per dry gram of syrup. Ammoniumbisulfite was a 65% aqueous solution of 95% ammonium bisulfite and 5%potassium bisulfite. The doses of the two reagents used were molarequivalent bisulfite doses. The reaction condition was carried out at85° C. for 30, 60 and 90 minutes.

FIG. 6 showed reduction of DON in syrup with ammonium bisulfite wassimilar to sodium bisulfite.

EXAMPLE 5

A test of SBS treatment in a grain-to-ethanol conversion process wasperformed in phases in which treatment was not conducted, and phases inwhich treatment was conducted. The data is shown in FIG. 7 . Syrup wasfed through a feed line into a syrup tank. The syrup was fed from thesyrup tank to the dryers where it combined with wet cake and was driedto produce DDGS. In Phase 1, no treatment was conducted and samples ofdried DDGS were collected and analyzed to measure the ppm of DONpresent. In Phase 2, 1.5 gallons per minute of a 38% aqueous solution ofSBS was supplied continuously into the feed line of the syrup tank andsamples of dried DDGS were collected and analyzed to measure the ppm ofDON present. In Phase 3, the flow of SBS was stopped and again untreatedsamples of dried DDGS were collected and analyzed to measure the ppm ofDON present. In Phase 4, 1 gallon per minute of a 38% aqueous solutionof SBS was supplied continuously into the feed line of the syrup tankand samples of dried DDGS were collected and analyzed to measure the ppmof DON present. FIG. 7 showed that the amount of DON in the DDGS wasreduced by approximately 40% to 50% when the SBS treatment system was inoperation.

EXAMPLE 6

A treated mycotoxin in which the DON levels in DON-contaminated DDGSwere reduced by the method described in Example 5 (1.5 gallons perminute of a 38% aqueous solution of SBS was supplied continuously intothe feed line of the syrup tank) and samples of dried DDGS werecollected, analyzed and tested for its effect on pig growth.

A total of 247 growing pigs (55.3±4.6 lb.) were housed at awean-to-finish facility, randomly allotted to 18 pens (13-14 pigs/pen)containing one 3-hole feeder 2 free-access nipple drinkers, and assignedto one of 3 experimental diets: control, DONDDGS, and treated-DDGS. Allexperimental diets were corn/soybean meal based containing 30% DDGS (lowDON, DON contaminated, and treated DON DDGS, respectively; Table 1).

TABLE 1 Levels of DON in the corn, DDGS sources and mixed diets on d0and 21¹. Item DON, ppm Corn 0.1 Clean DDGS (Control) 1.0 Treated DDGS(trtDDGS) 7.3 Untreated DDGS (DONDDGS) 11.6 d0 mixed diets Control 0.1trtDDGS 1.9 DONDGGS 3.0 d21 mixed diets Control 0.2 trtDDGS 2.6 DONDDGS3.0 ¹The DON value for corn is the mean of 3 corn samples (1 sample fromeach of the experimental diets). Diet samples were taken at mixing (d0)and from each feeder at the completion of the trial (d21).

All diets met or exceeded nutrient requirements for growing pigs basedon NRC (2012) and provided ad libitum. Experimental diets were fed for21 days. Samples of the DDGS and corn used in the diets were analyzedfor DON. Samples of the mixed diets were collected at day 0 and 21 andanalyzed for proximate analysis and DON.

Pigs were weighed individually on day 0, 3, 7, 10, 14, and 21. Feeddisappearance was determined simultaneously with pig weight.

Statistical analysis

Performance data were analyzed using the PROC MIXED procedure of SAS(Version 9.4; SAS Inst. Inc., Cary, NC) as a repeated measures modelwith pen as the random variable, weigh period as the repeated variable,and dietary treatment was the fixed effect. Weekly performance responseswere analyzed as a completely random design where differences betweentreatment means were tested using Tukey's adjusted means test when asignificant main effect was observed. Results were consideredsignificant at P<0.05 and tendency at 0.05>P<0.10.

Evidence of vomiting was observed within 4 hours of the experimentaldiets being available and was observed only in the DONDDGS pens.Vomiting was not observed beyond the first 24 hours of starting thetrial. Otherwise, pig health was good with only 1 pig removed prior tothe last day due to poor growth after repeated veterinary treatment.

Diet Mycotoxin Content

Negligible DON content was measured in the ground corn used for theexperimental diets. The level of DON in the ‘clean’ DDGS resulted in aDON level below the FDA recommended level (no greater than 1 ppm) in thecontrol diet. The sodium bisulfate treatment appeared to be effective atreducing the DON content in DON-DDGS by 37%, resulting in diet DONcontent of 1.9 ppm. The level of DON appeared stable in the control andDONDDGS diets with some increase in DONDDGS levels in the trtDDGS dietby the end of the 21 days.

Pig Performance

There was no main effect of diet on daily gain but a tendency (P=0.084)for an interaction between weigh period and diet where daily gain wasnot different between each weight period and lower (P<0.05) in the first3 days in pigs fed DONDDGS and trtDDGS compared to other weigh periods.Daily feed intake increased over time (P<0.0001) and there was atendency (P=0.071) for DONDDGS-fed pigs to have lower (P=0.029) overallintake compared to trtDDGS-fed. Overall intake was not different betweentrtDDGS- and Control-fed pigs.

1-20. (canceled)
 21. A process for remediating deoxynivalenol, wherein the process comprises: determining if deoxynivalenol is present in incoming grain and/or one or more biorefinery process compositions; and introducing one or more treatment compounds into at least one post-distillation, biorefinery process composition to react with at least a portion of the deoxynivalenol present in the at least one post-distillation, biorefinery composition to form a treated, post-distillation, biorefinery process composition comprising one or more reaction products, and reduce a concentration of the deoxynivalenol, wherein the at least one post-distillation, biorefinery process composition is chosen from whole stillage, thin stillage, syrup, and combinations thereof.
 22. The process of claim 21, wherein the determining comprises determining if the deoxynivalenol is present above a threshold concentration value in the incoming grain and/or in the one or more biorefinery process compositions, and wherein the introducing comprises introducing the one or more treatment compounds into the at least one post-distillation, biorefinery process composition to form a treated, post-distillation, biorefinery process composition if the deoxynivalenol is determined to be present above the threshold concentration value in the incoming grain and/or the one or more biorefinery process compositions.
 23. The process of claim 22, wherein the determining is performed upstream and/or downstream from where the one or more treatment compounds are introduced into the at least one post-distillation, biorefinery process composition.
 24. The process of claim 21, further comprising calculating a dose of the one or more treatment compounds to introduce into the at least one post-distillation, biorefinery process composition based on a determined concentration of the deoxynivalenol.
 25. The process of claim 21, further comprising: milling grain to form milled grain; forming slurry comprising water and the milled grain; fermenting sugar present in the slurry to produce beer by converting the sugar into biochemical via a microorganism; distilling the beer to separate the biochemical from the beer and form the whole stillage; separating the thin stillage and wet cake from the whole stillage; exposing at least a portion of the thin stillage to an evaporator system to remove moisture from the thin stillage and form the syrup.
 26. The process of claim 25, wherein the one or more treatment compounds comprise one or more sulfur-containing compounds, and wherein the one or more treatment compounds react with the at least a portion of the deoxynivalenol present in the at least one post-distillation, biorefinery composition to form deoxynivalenol sulfonate.
 27. The process of claim 26, wherein the one or more sulfur-containing compounds are chosen from potassium bisulfite, sodium bisulfite and combinations thereof
 28. A process for remediating deoxynivalenol, wherein the process comprises: determining if deoxynivalenol is present in incoming grain and/or one or more biorefinery process compositions; separating whole stillage into thin stillage and wet cake; evaporating moisture from the thin stillage to form syrup; separating the syrup into a first oil fraction and a first aqueous fraction; and separating the first oil fraction into a second oil fraction and a second aqueous fraction; introducing one or more treatment compounds into at least one post-distillation, biorefinery process composition to react with at least a portion of the deoxynivalenol present in the at least one post-distillation, biorefinery composition to form a treated, post-distillation, biorefinery process composition comprising one or more reaction products, and reduce a concentration of the deoxynivalenol, wherein the at least one post-distillation, biorefinery process composition is chosen from the first aqueous fraction, the second aqueous fraction, the first oil fraction, the second oil fraction, and combinations thereof.
 29. The process of claim 28, wherein the at least one post-distillation, biorefinery process composition is chosen from the first aqueous fraction, the second aqueous fraction, and combinations thereof, and further comprising combining the first aqueous fraction and/or the second aqueous fraction with the wet cake to form distillers' grain product.
 30. The process of claim 21, further comprising: separating a portion of the thin stillage to be used as backset; and downstream from separating the portion of the thin stillage, introducing the one or more treatment compounds into the remainder of the thin stillage and/or the syrup.
 31. The process of claim 27, wherein the at least one post-distillation, biorefinery process composition comprises syrup, and wherein the one or more treatment compounds are introduced into the syrup in amount from 0.01 to about 0.05 grams of the one or more treatment compounds per dry gram of the syrup.
 32. The process of claim 27, wherein the at least one post-distillation, biorefinery process composition comprises syrup, and wherein the one or more treatment compounds are introduced into piping that transports the syrup.
 33. The process of claim 27, wherein the at least one post-distillation, biorefinery process composition comprises syrup, and wherein the one or more treatment compounds are introduced into a syrup tank located downstream from the evaporator system.
 34. The process of claim 29, wherein the at least one post-distillation, biorefinery process composition comprises the second aqueous fraction, and wherein one or more treatment compounds are introduced into piping that transports the first aqueous fraction and/or the second aqueous fraction.
 35. The process of claim 21, wherein the at least one post-distillation, biorefinery process composition is at a temperature in a range from 30° C. to 120° C. at least after introduction of the one or more treatment compounds.
 36. The process of claim 21, wherein the at least one post-distillation, biorefinery process composition is at a temperature in a range from 80° C. to 90° C. at least after introduction of the one or more treatment compounds.
 37. The process of claim 21, wherein the one or more treatment compounds are introduced into the at least one post-distillation, biorefinery process composition in amount from 0.05% to about 5% by weight of the at least one post-distillation, biorefinery process composition.
 38. The process of claim 21, wherein the concentration of the deoxynivalenol is reduced to less than 5 ppm in the treated, post-distillation, biorefinery process composition by introducing the one or more treatment compounds into the at least one post-distillation, biorefinery process composition.
 39. The process of claim 21, wherein the concentration of the deoxynivalenol is reduced by at least 30 percent in the treated, post-distillation, biorefinery process composition by introducing the one or more treatment compounds into the at least one post-distillation, biorefinery process composition.
 40. The process of claim 25, further comprising forming distillers' grain product from the wet cake and the syrup.
 41. The process of claim 26, wherein the one or more sulfur-containing compounds are chosen from ammonium bisulfite, potassium bisulfite, sodium bisulfite and combinations thereof.
 42. The process of claim 23, wherein the introducing the one or more treatment compounds into the at least one post-distillation, biorefinery process composition is performed on an intermittent basis.
 43. The process of claim 42, wherein the introducing the one or more treatment compounds is continued while the deoxynivalenol is present above the threshold concentration value and the introducing the one or more treatment compounds is discontinued when the deoxynivalenol is present below the threshold concentration value.
 44. The process of claim 21, further comprising: providing a remediation system having a reactant storage system comprising the one or more treatment compounds and a dispensing system in fluid communication with the reactant storage system, wherein the dispensing system is fluidly coupled to the at least one post-distillation, biorefinery process composition to introduce an amount of the one or more treatment compounds into the at least one post-distillation, biorefinery process composition to form the treated, post-distillation, biorefinery process composition.
 45. The process of claim 33, further comprising: providing a remediation system having a reactant storage system comprising the one or more treatment compounds and a dispensing system in fluid communication with the reactant storage system, wherein the dispensing system is fluidly coupled to piping that transports the first aqueous fraction to introduce an amount of the one or more treatment compounds into the first aqueous fraction to form treated first aqueous fraction.
 46. The process of claim 44, wherein the providing the remediation system comprises providing the remediation system in a portable skid mounted configuration.
 47. The process of claim 44, further comprising operating the dispensing system to adjust a dose of the one or more treatment compounds that is to be introduced into the at least one post-distillation, biorefinery process compositions.
 48. The process of claim 44, further comprising operating the dispensing system to introduce an aqueous solution comprising the one or more treatment compounds.
 49. The process of claim 44, further comprising operating the dispensing system to introduce the amount of the one or more treatment compounds into the at least one post-distillation, biorefinery process composition on an intermittent basis.
 50. The process of claim 44, further comprising: providing a measurement system configured to determine a level of the deoxynivalenol; operating the measurement system to determine whether the deoxynivalenol is present above a threshold concentration value upstream and/or downstream from where the dispensing system is fluidly coupled to the at least one post-distillation, biorefinery process composition; and operating the dispensing system to introduce the amount of the one or more treatment compounds into the at least one post-distillation, biorefinery process composition to form a treated, post-distillation, biorefinery process composition if the deoxynivalenol is determined to be present above the threshold concentration value. 